Concentration Of Free Radicals Research Articles

Multihierarchical Regulation To Achieve Quantum Dot Nanospheres with a Photoluminescence Quantum Yield Close to 100.

Quantum dots (QDs) exhibit superior brightness and photochemical stability, making them the preferred option for highly sensitive single-molecule detection compared with fluorescent dyes or proteins. Nevertheless, their high surface energy leads to nonspecific adsorption and poor colloidal stability. In the past decades, we have found that QD-based fluorescent nanoparticles (FNs) can not only address these limitations but also enhance detection sensitivity. However, the photoluminescence quantum yield (PLQY) of FNs is significantly lower compared with that of original QDs. It is urgent to develop a strategy to solve the issue, aiming to further enhance detection sensitivity. In this study, we found that the decrease of PLQY of FNs prepared by free radical polymerization was attributed to two factors: (1) generation of defects that can cause nonradiative transitions resulting from QD-ligands desorption and QD-shell oxidation induced by free radicals; (2) self-absorption resulting from aggregation caused by incompatibility of QDs with polymers. Based on these, we proposed a multihierarchical regulation strategy that includes: (1) regulating QD-ligands; (2) precisely controlling free radical concentration; and (3) constructing cross-linked structures of polymer to improve compatibility and to reduce the formation of surface defects. It is crucial to emphasize that the simultaneous coordination of multiple factors is essential. Consequently, a world-record PLQY of 97.6% for FNs was achieved, breaking through the current bottleneck at 65%. The flexible application of this regulatory concept paves the way for the large-scale production of high-brightness QD-polymer complexes, enhancing their potential applications in sensitive biomedical detection.

Reaction mechanism of antioxidant inhibition of hydroxyl radical in coal oxidation.

To solve the problem of unclear targeted inhibition of key free radicals by antioxidants, this paper took the hydroxyl radical with the highest oxidation activity of coal as the inhibition target and selected five antioxidants such as ethylene diamine tetraacetic acid, tea polyphenol, citric acid, vitamin C, and proanthocyanidins. Based on the theory of quantum chemistry, the characteristics and oxidation pathway of antioxidants inhibiting coal oxidation of hydroxyl radical were analyzed. Analyze the influence characteristics of antioxidants on the evolution of free radicals in coal through an electron paramagnetic resonance experiment (ESR). The results showed that the electron density of antioxidants was mainly distributed in the functional groups of carboxyl and hydroxyl, which played a key inhibitory role, and the vicinity of carboxyl and hydroxyl and other functional groups was positive potential, which was the active site of inhibiting hydroxyl radical. The order of inhibitory capacity of the five antioxidants was determined as GTP > PC > EDTA > CA > VC. It is concluded that the energy barrier of hydroxyl radical inhibition by citric acid is much lower than that of EDTA. For the hydrogen extraction reaction, VC inhibited the hydroxyl radical pathway with a higher energy barrier than the other three antioxidants. The mechanism of five antioxidants inhibiting •OH reaction was comprehensively analyzed. It was found that tea polyphenols have more active sites that can react with •OH to quench it, so the inhibition of tea polyphenols should be the most significant. When antioxidants inhibit coal spontaneous combustion, the type, complexity, concentration, and linewidth of free radicals in coal molecules are lower than those in raw coal, with GTP antioxidants having the best inhibitory effect. The research results have important theoretical and practical significance for revealing the mechanism of coal spontaneous combustion inhibition and developing directional coal spontaneous combustion inhibition technology.

Unlocking clean gas with hydrogen: A combustion optimization study

Combining hydrogen with natural gas, a hydrocarbon fuel, is seen as a critical step towards reaching net-zero emissions and creating a cleaner environment. To tackle climate change, major organizations like the U.S. Department of Energy, Energy Innovation, and the International Renewable Energy Agency are promoting the use of hydrogen blended with natural gas. This approach can potentially cut emissions in half compared to relying solely on natural gas. Using the Ansys 2022 R1 CHEMKIN tool, the study analyses combustion features in H2-CNG (compressed natural gas) -air mixtures, considering atmospheric conditions and operational parameters. Blending 50 % hydrogen with CNG results in significant changes, including an increase in laminar flame speed from 48.78 cm/s to 71.52 cm/s. As the hydrogen content in the CNG blend increases from 0 to 50 %, the concentration of free radicals like H, O, and OH rises by 42.86 %, 28.57 %, and 20.00 %, respectively, reaching these values at a 50 % hydrogen blend compared to pure CNG. NSGA-II multi-objective optimization identified that a 50 % hydrogen-blended CNG surpasses pure CNG in laminar flame speed and free radical generation. The research confirms that H2-CNG creates a promising fuel with several advantages. When combusted, H2-CNG mixtures exhibit superior characteristics, including potentially increased efficiency through increased free radical formation and laminar flame speed. This innovation has the potential to significantly reduce carbon footprint and contribute to achieving carbon neutrality goals. The cleaner and more efficient combustion properties of H2-CNG offer a compelling pathway for mitigating climate change.

Redox-Active Compounds in the Therapy of Drug-Resistant Murine Leukemia P388 Strains.

The efficiency of combinations of cytostatics cisplatin and adriamycin with antioxidant sodium 3-(3'-tert-butyl-4-hydroxyphenyl)propyl thiosulfate (TS-13), and nitric oxide (NO) donor NaNO2 was evaluated on two drug-resistant strains of leukemia P388 with changed redox-status of cells. Simultaneous use of both NO donor and TS-13 in combinations with the cytostatics did not increase the efficiency of therapy. In addition, antioxidant activity of TS-13, NaNO2, and their combinations was studied by the method of luminol-dependent chemiluminescence on the model systems with the use of the homogenized cells of sensitive strain and two drug-resistant strains of leukemia P388. It was shown that TS-13 and NO donor produced opposite effects: TS-13 decreased, while NO donor increased the content of free radicals in the model system. Combinations of antioxidant TS-13 and NO donor should be used with consideration for the redox-status of tumor treated.

Elucidating the mechanism on carbon nanotube-coated cobalt phosphide catalyst activating PMS to degrade norfloxacin contaminants

Transition metal phosphides have shown great potentials in persulfate activation for eliminating organic contaminants, while the understanding of the activation mechanism still remains fragmentary. Herein, a series of nitrogen-phosphorus-doped carbon nanotube-coated cobalt phosphide catalysts (Co/P-CNTs) were synthesized for activating peroxymonosulfate (PMS) to degrade norfloxacin (NOR). The optimal Co/P-CNTs-0.3 could eliminate NOR up to 97 % within 60 min in the presence of PMS. Results confirm that the synergistic interaction between multi-valent Co species in the Co/P-CNTs significantly contributes to the excellent PMS activation performance. The contribution of reactive oxygen species (ROS) to pollutant removal and the steady-state concentration of free radicals were quantitatively analyzed by means of chemical probe and reaction kinetics. A free radical mechanism dominated by SO4•– and NOR degradation pathway were identified, and the effect of coexisting inorganic anions was systematically evaluated. This study offers profound insights into the activation mechanism of metal phosphides towards environmental remediation.

Liraglutide Protects Cardiomyocytes against Isoprenaline-Induced Apoptosis in Experimental Takotsubo Syndrome.

Takotsubo syndrome (TTS) is a stress-induced cardiomyopathy, characterized by an increased concentration of catecholamines, free radicals, and inflammatory cytokines, endothelial dysfunction, and increased apoptotic activity. High doses of isoprenaline are used in animal models to induce Takotsubo (TT)-like myocardial injury. The aim of the study was to investigate the antiapoptotic effects of liraglutide in experimental TTS and its role in the NF-κB pathway. Wistar rats were pretreated with liraglutide for 10 days, and on days 9 and 10, TT-like myocardial injury was induced with isoprenaline. After the sacrifice on day 11, hearts were isolated for histopathological and immunohistochemical analysis. Liraglutide reduced isoprenaline-induced cardiomyocyte apoptosis by decreasing cleaved caspase-3 (CC3), BCL-2-associated X protein (BAX), and NF-κB and increasing B-cell lymphoma/leukemia-2 (BCL-2). An increase in NF-κB in isoprenaline-treated rats was in positive correlation with proapoptotic markers (BAX and CC3) and in negative correlation with antiapoptotic marker BCL-2. Liraglutide increased BCL-2 and decreased NF-κB, BAX, and CC3, preserving the same correlations of NF-κB to apoptotic markers. It is concluded that liraglutide protects cardiomyocytes against isoprenaline-induced apoptosis in experimental TT-like myocardial injury through downregulation of the NF-κB pathway.

Prevention of cyclophosphamide-induced immune suppression by polysaccharides from Apocynum venetum flowers via enhancing immune response, reducing oxidative stress, and regulating gut microbiota in mice

IntroductionEmerging proof suggests that Apocynum venetum flowers polysaccharide (AVFP) has immunomodulatory effects in vitro. However, the action mechanism of AVFA is still unclear in vivo. The purpose of this study is to probe into the potential mechanism of AVFA in immunosuppressed mice by investigating organ index, cytokine levels, anti-oxidative stress capacity, transcriptomics, and gut microbiota.MethodsImmunocompromised mice induced by cyclophosphamide (CTX) were divided into six groups. The enzyme-labeled method, hematoxylin and eosin, transcriptomics, and high-throughput sequencing were used to detect the regulatory effects of AVFP on immunocompromised mice and the function of AVFP on the concentration of short-chain fatty acids (SCFAs) by high-performance liquid chromatography (HPLC) analysis. The Spearman correlation analysis was used to analyze the correlation between the intestinal microbiota and biochemical indexes.ResultsThe experimental results illustrated that AVFP has protective effects against CTX-induced immunosuppression in mice by prominently increasing the organ index and levels of anti-inflammatory factors in serum in addition to enhancing the antioxidant capacity of the liver. Meanwhile, it could also signally decrease the level of pro-inflammatory cytokines in serum, the activity of transaminase in serum, and the content of free radicals in the liver, and alleviate the spleen tissue damage induced by CTX. Transcriptomics results discovered that AVFP could play a role in immune regulation by participating in the NF-κB signaling pathway and regulating the immune-related genes Bcl3, Hp, Lbp, Cebpd, Gstp2, and Lcn2. Gut microbiota results illustrated that AVFP could increase the abundance of beneficial bacteria, reduce the abundance of harmful bacteria, and regulate the metabolic function of intestinal microorganisms while dramatically improving the content of SCFAs, modulating immune responses, and improving the host metabolism. The Spearman analysis further evaluated the association between intestinal microbiota and immune-related indicators.ConclusionThese findings demonstrated that AVFP could enhance the immune effects of the immunosuppressed mice and improve the body’s ability to resist oxidative stress.

BR regulates wheat root salt tolerance by maintaining ROS homeostasis.

Trace amounts of epibrassinolide (EpiBL) could partially rescue wheat root length inhibition in salt-stressed situation by scavenging ROS, and ectopic expression of TaDWF4 or TaBAK1 enhances root salt tolerance in Arabidopsis by balancing ROS level. Salt stress often leads to ion toxicity and oxidative stress, causing cell structure damage and root development inhibition in plants. While prior research indicated the involvement of exogenous brassinosteroid (BR) in plant responses to salt stress, the precise cytological role and the function of BR in wheat root development under salt stress remain elusive. Our study demonstrates that 100mM NaCl solution inhibits wheat root development, but 5nM EpiBL partially rescues root length inhibition by decreasing H2O2 content, oxygen free radical (OFR) content, along with increasing the peroxidase (POD) and catalase (CAT) activities in salt-stressed roots. The qRT-PCR experiment also shows that expression of the ROS-scavenging genes (GPX2 and CAT2) increased in roots after applying BR, especially during salt stress situation. Transcriptional analysis reveals decreased expression of BR synthesis and root meristem development genes under salt stress in wheat roots. Differential expression gene (DEG) enrichment analysis highlights the significant impact of salt stress on various biological processes, particularly "hydrogen peroxide catabolic process" and "response to oxidative stress". Additionally, the BR biosynthesis pathway is enriched under salt stress conditions. Therefore, we investigated the involvement of wheat BR synthesis gene TaDWF4 and BR signaling gene TaBAK1 in salt stress responses in roots. Our results demonstrate that ectopic expression of TaDWF4 or TaBAK1 enhances salt tolerance in Arabidopsis by balancing ROS (Reactive oxygen species) levels in roots.

Energy deprivation affects nitrogen assimilation and fatty acid biosynthesis leading to leaf chlorosis under waterlogging stress in the endangered Abies koreana.

Energy deprivation triggers various physiological, biochemical and molecular changes in plants under abiotic stress. We investigated the oxidative damages in the high altitude grown conifer Korean fir (Abies koreana) exposed to waterlogging stress. Our experimental results showed that waterlogging stress led to leaf chlorosis, 35days after treatment. A significant decrease in leaf fresh weight, chlorophyll and sugar content supported this phenotypic change. Biochemical analysis showed a significant increase in leaf proline, lipid peroxidase and 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical content of waterlogged plants. To elucidate the molecular mechanisms, we conducted RNA-sequencing (RNA-seq) and de novo assembly. Using RNA-seq analysis approach and filtering (P<0.05 and false discovery rate<0.001), we obtained 134 unigenes upregulated and 574 unigenes downregulated. Gene Ontology and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analysis placed the obtained differentially expressed unigenes in α-linoleic pathway, fatty acid degradation, glycosis, glycolipid metabolism and oligosaccharide biosynthesis process. Mapping of unigenes with Arabidopsis using basic local alignment search tool for nucleotides showed several critical genes in photosynthesis and carbon metabolism downregulated. Following this, we found the repression of multiple nitrogen (N) assimilation and nucleotide biosynthesis genes including purine metabolism. In addition, waterlogging stress reduced the levels of polyunsaturated fatty acids with a concomitant increase only in myristic acid. Together, our results indicate that the prolonged snowmelt may cause inability of A. koreana seedlings to lead the photosynthesis normally due to the lack of root intercellular oxygen and emphasizes a detrimental effect on the N metabolic pathway, compromising this endangered tree's ability to be fully functional under waterlogging stress.

Comprehensive studies on the biological activities of human metastatic (MDA-MB-231) and non-metastatic (MCF-7) breast cancer cell lines, directly or combinedly treated using non-thermal plasma-based approaches

Progressive incidence and a pessimistic survival rate of breast cancer in women worldwide remains one of the most concerning topics. Progressing research indicates a potentially high effectiveness of use cold atmospheric plasma (CAP) systems. The undoubted advantage seems its simplicity in combination with other anti-cancer modalities. Following observed trend of studies, one inventory CAP system was applied to directly treat human breast cancer cell lines and culturing in two different Plasma Activated Media (PAM) for combined utilization. Proposed CAP treatments on MCF-10 A, MCF-7, and MDA-MB-231 cell lines were studied in terms of impact on cell viability by MTT assay. Disturbances in cell motility following direct and combined CAP application were assessed by scratch test. Finally, the induction of apoptosis and necrosis was verified with annexin V and propidium iodide staining. Reactive species generated during CAP treatment were determined based on optical emission spectrometry analysis along with colorimetric methods to qualitatively assess the NO2−, NO3−, H2O2, and total ROS with free radicals concentration. The most effective approach for CAP utilization was combined treatment, leading to significant disruption in cell viability, motility and mostly apoptosis induction in breast cancer cell lines. Determined CAP dose allows for mild outcome, showing insignificant harm for the non-cancerous MCF-10 A cell line, while the highly aggressive MDA-MB-231 cell line shows the highest sensitivity on proposed CAP treatment. Direct CAP treatment seems to drive the cells into the sensitive state in which the effectiveness of PAM is boosted. Observed anti-cancer response of CAP treatment was mostly triggered by RNS (mostly NO2− ions) and ROS along with free radicals (such as H2O2, OH•, O2-•, 1O2, HO2•). The combined application of one CAP source represent a promising alternative in the development of new and effective modalities for breast cancer treatment.

Streptomycin generates oxidative stress in melanin-producing cells: In vitro study with EPR spectroscopy evidence

Streptomycin (STR) is an aminoglycoside antibiotic with a broad-spectrum of activity and ototoxic potential. The mechanism of STR-induced inner ear damage has not been fully elucidated. It was previously found that STR binds to melanin, which may result in the accumulation of the drug in melanin-containing tissues. Melanin pigment is present in various parts of the inner ear, including the cochlea and vestibular organ.The present study aimed to assess if streptomycin generates oxidative stress and affects melanogenesis in normal human melanocytes. Moreover the variation of free radical concentration in STR-treated melanocytes was examined by electron paramagnetic resonance spectroscopy (EPR). We found that STR decreases cell metabolic activity and reduces melanin content. The observed changes in the activity of antioxidant enzymes activity in HEMn-DPs treated with streptomycin may suggest that the drug affects redox homeostasis in melanocytes. In this work EPR study expanded knowledge about free radicals in interactions of STR and melanin in melanocytes. The results may help elucidate the mechanisms of STR toxicity on pigment cells, including melanin-producing cells in the inner ear. This is important because understanding the mechanism of STR-induced ototoxicity would be helpful in developing new therapeutic strategies to protect patients' hearing.

Studies of the diluent, temperature and pressure effect on the lower and upper flammability limits of ammonia in air

Ammonia safety and environmental protection research forms the basis for its role as a clean energy carrier. In this work, an experimental study was conducted in this work to analyze the effect of different inhibitors (nitrogen, argon and water vapor) on the flammability limits (FLs) of ammonia at elevated temperatures and pressures. In addition, the influence of diluents on the compositions and flame temperature changes was evaluated, and the temperature sensitivity coefficients of the elementary reactions and the ROP of free radicals and partial products at the FL concentrations were analyzed. The findings indicated that water vapor provided the strongest flame retardant effect on ammonia in three inhibitors. Within a certain temperature and pressure range, the FLs of ammonia in ammonia/diluent/air can be predicted using the extended Le Chatelier equation. The flame temperature decreased at the lower flammability limit (LFL) concentrations and increased at the upper flammability limit (UFL) concentrations of ammonia with increasing initial pressure. As the initial temperature increases, the flame temperature decreases during ammonia combustion. The influence of ammonia concentration on flame temperature is greater than that of diluents dilution. The elementary reactions H+O2<=>O+OH (R1) and NH2+NO<=>NNH+OH (R82) were the primary reactions that increased the flame temperature at the FL ammonia concentrations in ammonia/diluent/air. Conversely, NH2+NO<=>N2+H2O (R80) and H+O2(+M)<=>HO2(+M)(R15) were the main reactions that decreased the flame temperature. H, OH and NH2 radicals played a crucial role in the combustion reaction process at ammonia FL concentrations. At the LFL concentrations of ammonia, the molar fraction of the OH radical showed the greatest variation, while at the UFL concentrations of ammonia it was NH2 radical. The elementary reaction NH3+OH<=>NH2+H2O (R158) was the primary reaction that consumed OH radical and promoted the formation of NH2 radical. Free radical concentrations decreased with increasing pressure and temperature, while the change rate of free radical ROP accelerated with increasing pressure. In addition to nitrogen and water, the partial products were mainly nitric oxide at the LFL concentrations, while at the UFL concentrations were mainly hydrogen.

Study on ignition mechanism of turbulent jet pre-chamber of H2/CO mixture

Jet flow pre-chamber ignition is used to increase the thermal efficiency of lean-burn engines, but the ignition mechanism in the main chamber remains unclear. Therefore, the ignition mechanism of the jet pre-chamber was investigated experimentally and numerically. The results show that the flame in the pre-chamber can indeed propagate to the main chamber through a 2-mm-diameter nozzle without extinguishing. This occurs because at the very start the flame is located in the center of the nozzle and maintains a certain distance from the wall, preserving both temperature and free radicals. Next the flame in the nozzle will be extinguished due to fuel depletion, leading to a significant reduction in the concentration of free radicals. The free radicals pass through the nozzle, and compared with only the hot ignition, the ignition in the main chamber is one preparation period earlier, indicating a more concentrated heat release and higher thermal conversion ability in real engines.

Free radical production induced by visible light in live fruit flies

Visible light triggers free radical production in alive and intact Drosophila melanogaster. We exposed fruit flies to red (613–631 nm), green (515–535 nm), and blue (455–475 nm) light while we monitored changes in unpaired electron content with an electron spin resonance spectrometer (ESR/EPR). The immediate response to light is a rapid increase in spin content lasting approximately 10 s followed by a slower, linear increase for approximately 170 s. When the light is turned off, the spin population promptly decays with a similar time course, though never fully returning to baseline. The magnitude and time course of the spin production depends on the wavelength of the light. Initially, we surmised that eumelanin might be responsible for the spin change because of its documented ability for visible light absorption and its highly stable free radical content. To explore this, we utilized different fruit fly strains with varying eumelanin content and clarified the relation of melanin types with the spin response. Our findings revealed that flies with darker cuticle have at least three-fold more unpaired electrons than flies with yellow cuticle. However, to our surprise, the increase in unpaired electron population by light was not drastically different amongst the genotypes. This suggests that light-induced free radical production may not exclusively rely on the presence of black melanin, but may instead be dependent on light effects on quinone-based cuticular polymers.

Antioxidant activity of polyphenol compounds extracted from Nypa fruticans Wurmb. (Nipa palm) fruit husk with different ethanol concentration

Oxidative stress is a condition characterized by a higher content of free radicals than the potential antioxidants in the body. Exogenous antioxidants are needed to resolve this condition. The Nypa fruticans (Nipa palm) fruit husk is a source of polyphenol potential and can be used as a natural antioxidant agent. Therefore, this study aimed to determine the effect of ethanol concentration on polyphenol and tannin contents and their antioxidant activities. The polyphenol substances were extracted using several ethanol concentrations, whereas the antioxidant activity was determined using the 2,2-diphenyl-1-picrylhydrazyl method. The results show that the ethanol concentration has no effect on the yield of extraction. However, it affects the total polyphenol and tannin contents with high levels in the 50% and 70% ethanol concentrations. Fifty percent ethanol exhibits more effective antioxidant activity when compared to other ethanol concentrations. Therefore, a 50% ethanol concentration is a suitable solvent to extract polyphenol and tannin substances from nipa palm fruit husk and can be used as an alternative natural antioxidant.

PH-responsive HMDS terminated m-Cresol for inhibiting the spontaneous combustion in different-rank coals

In this study, pH responsiveness of 1, 1, 1, 3, 3, 3-hexamethyldisilazane terminated m-Cresol (HTMC) in different-rank coals was investigated, and its inhibition performance regarding the spontaneous combustion of coal was explored. First, color changes in the deprotection reaction of HTMC under different acidic conditions were analyzed. Then, surface microstructures of these coals and pH values of their filtrates were tested. Subsequently, experiments were performed on different coal samples for grasping their low-temperature oxidation characteristics, weight loss rates, pore characteristics, and free radical variations. The experimental results show that HTMC can effectively protect phenolic hydroxyl groups in inhibitors, and the acidity of coal can promote the conversion rate of its deprotection reaction. For instance, in XAM coal (pH ≈ 6), sufficient H+ stimulates HTMC to release massive m-Cresol which contains highly reactive phenolic hydroxyl, thereby effectively suppressing increases of the concentration and type of free radicals. The crossing point temperature (177.2 °C) and inhibition rate at 110 °C (75.9 %) of the HTMC-inhibited XAM sample are 33.1 °C and 17.9 % higher than those of the m-Cresol-inhibited one, respectively. This study confirms the applicability of pH-responsive HTMC to different-rank coals and may lay a theoretical foundation for the design of efficient reactive inhibitors.

Effects of different thermal sterilization conditions on the quality of ready-to-eat shrimp based on specific sterilization intensity

The effects of different thermal sterilization conditions on the quality and digestibility of ready-to-eat (RTE) shrimp were investigated. Compared with the high-temperature (121 °C) and short-time (6 min and 8 min) sterilization, the low-temperature (110 and 115 °C) and long-time (>20 min) sterilization significantly promoted the Maillard and browning reactions and changed the color of the RTE-shrimp. The high sterilization temperature promoted shrimp protein oxidation, resulting in increased carbonyl group, disulfide bond, and free radical content, while the free sulfhydryl group content decreased. This oxidation and tissue destruction at high temperature led to reduced texture properties and altered water distribution within the shrimp's muscles. However, sterilized shrimp exhibited superior digestive properties in an in vitro simulated digestion experiment. High-temperature and short-time sterilization is more effective in mitigating the quality deterioration of RTE-shrimp compared to low-temperature and long-time sterilization.

Releasing Free Radicals in Precursor Triggers the Formation of Closed Pores in Hard Carbon for Sodium-Ion Batteries.

Increasing closed pore volume in hard carbon is considered to be the most effective way to enhance the electrochemical performance in sodium-ion batteries. However, there is a lack of systematic insights into the formation mechanisms of closed pores at molecular level. In this study, a regulation strategy of closed pores via adjustment of the content of free radicals is reported. Sufficient free radicals are exposed by part delignification of bamboo, which is related to the formation of well-developed carbon layers and rich closed pores. In addition, excessive free radicals from nearly total delignification lead to more reactive sites during pyrolysis, which competes for limited precursor debris to form smaller microcrystals and therefore compact the material. The optimal sample delivers a large closed pore volume of 0.203 cm3 g-1, which leads to a high reversible capacity of 350 mAh g-1 at 20 mA g-1 and enhanced Na+ transfer kinetics. This work provides insights into the formation mechanisms of closed pores at molecular level, enabling rational design of hard carbon pore structures.

Biochar-Derived Persistent Free Radicals: A Plethora of Environmental Applications in a Light and Shadows Scenario.

Biochar (BC) is a carbonaceous material obtained by pyrolysis at 200-1000 °C in the limited presence of O2 from different vegetable and animal biomass feedstocks. BC has demonstrated great potential, mainly in environmental applications, due to its high sorption ability and persistent free radicals (PFRs) content. These characteristics enable BC to carry out the direct and PFRs-mediated removal/degradation of environmental organic and inorganic contaminants. The types of PFRs that are possibly present in BC depend mainly on the pyrolysis temperature and the kind of pristine biomass. Since they can also cause ecological and human damage, a systematic evaluation of the environmental behavior, risks, or management techniques of BC-derived PFRs is urgent. PFRs generally consist of a mixture of carbon- and oxygen-centered radicals and of oxygenated carbon-centered radicals, depending on the pyrolytic conditions. Here, to promote the more productive and beneficial use of BC and the related PFRs and to stimulate further studies to make them environmentally safer and less hazardous to humans, we have first reviewed the most common methods used to produce BC, its main environmental applications, and the primary mechanisms by which BC remove xenobiotics, as well as the reported mechanisms for PFR formation in BC. Secondly, we have discussed the environmental migration and transformation of PFRs; we have reported the main PFR-mediated application of BC to degrade inorganic and organic pollutants, the potential correlated environmental risks, and the possible strategies to limit them.

Deduction of lignite liquefaction mechanism based on carbon structure analysis and free radical determination

The liquefaction performance of lignite is closely related to its structural evolution. The carbon structure and the free radical concentrations of Naomaohu (NMH) coal and liquefaction products were characterized by modified nuclear magnetic resonance (NMR) spectroscopy and electron paramagnetic resonance (EPR), respectively. The results showed that the oil yield increased gradually with the increase in temperature, and it reached a maximum of 64.91% at 430 °C. The carbon spectrum of the liquefied oil showed that the increase in temperature had little effect on the aromatic carbon connected with the aliphatic carbon, but had a greater effect on the aromatic proton carbon of the liquefied oil. The stability of aromatic carbon in asphaltene was greater than that of aliphatic carbon, and the temperature rise had a significant impact on the different types of aliphatic carbon of the asphaltene. The aromatic side chain of asphaltene gradually broke, and the bridgehead carbon content of the aromatic carbon increased due to the intensification of the condensation reaction at high temperature. On the other hand, the concentration of free radicals in liquefied oil increased with temperature, while the concentration of free radicals in asphaltene first increased and then decreased with temperature, indicating a positive correlation between its change trend and respective yield. With the increase in temperature, the aromatic ring substances with strong bond energy were gradually opened, the side chains were broken, thus forming more low molecular compounds. In summary, based on the above changes in the carbon structure and free radicals, the lignite pyrolysis and liquefaction mechanism have been deduced at the molecular level.